Xiufeng Lang

A facile way to rejuvenate Ag3PO4 as a recyclable highly efficient photocatalyst.

Recycling awarded the silver: Ag(3)PO(4), a highly efficient photocatalyst, decomposes to the weak photocatalyst Ag during consecutive photocatalytic cycles. A facile and very mild wet chemical oxidation method was proposed, which involves the cooperation of H(2)O(2) with Na(2)HPO(4), to rejuvenate Ag(3)PO(4) from Ag as a recyclable highly efficient photocatalyst.

Localized Excitation of Ti3+ Ions in the Photoabsorption and Photocatalytic Activity of Reduced Rutile TiO2

In reduced TiO2, electronic transitions originating from the Ti(3+)-induced states in the band gap are known to contribute to the photoabsorption, being in fact responsible for the materials blue color, but the excited states accessed by these transitions have not been characterized in detail. In this work we investigate the excited state electronic structure of the prototypical rutile TiO2(110) surface using two-photon photoemission spectroscopy (2PPE) and density functional theory (DFT) calculations. Using 2PPE, an excited resonant state derived from Ti(3+) species is identified at 2.5 ± 0.2 eV above the Fermi level (EF) on both the reduced and hydroxylated surfaces. DFT calculations reveal that this excited state is closely related to the gap state at ∼1.0 eV below EF, as they both result from the Jahn-Teller induced splitting of the 3d orbitals of Ti(3+) ions in reduced TiO2. Localized excitation of Ti(3+) ions via 3d → 3d transitions from the gap state to this empty resonant state significantly increases the TiO2 photoabsorption and extends the absorbance to the visible region, consistent with the observed enhancement of the visible light induced photocatalytic activity of TiO2 through Ti(3+) self-doping. Our work reveals the physical origin of the Ti(3+) related photoabsorption and visible light photocatalytic activity in prototypical TiO2 and also paves the way for the investigation of the electronic structure and photoabsorption of other metal oxides.

Polyhedral AgBr Microcrystals with an Increased Percentage of Exposed {111} Facets as a Highly Efficient Visible‐Light Photocatalyst

Synthesis of inorganic single crystals with exposed high-reactivity facets is a desirable target in the catalytic chemistry field. Polyhedral AgBr microcrystals with an increased percentage of exposed high-reactivity {111} facets have been successfully prepared for the first time, and the photocatalytic performance of these microcrystals when used as an AgBr/Ag plasmonic photocatalyst was investigated. The results indicate that the as-prepared sample has high photocatalytic activity and, under the same measurement conditions, the photodegradation rate of methyl orange dye over these microcrystals is at least four times faster than with other shapes of AgBr/Ag microstructure, as well as 20 times faster than with the highly efficient Ag(3)PO(4) photocatalyst. DFT calculations suggest that the AgBr (111) surface is mainly composed of unsaturated Ag atoms and has a relatively high surface energy, both of which are favorable for enhancing the photocatalytic activity of the AgBr/Ag polyhedron photocatalyst. This work not only provides a highly efficient plasmonic photocatalyst of polyhedral AgBr/Ag microcrystals with an increased percentage of exposed high-reactivity AgBr {111} facets, but also demonstrates that the shape and crystalline quality of the exposed facets have an important influence on the photocatalytic activities.

β-MnO2 as a cathode material for lithium ion batteries from first principles calculations

The search for excellent cathodes for lithium batteries is the main topic in order to meet the requirements of low cost, high safety, and high capacity in many real applications. β-MnO2, as a potential candidate, has attracted great attention because of its high stability and potential high capacity among all the phases. Because of the complexity of β-MnO2, some fundamental questions at the atomic level during the charge-discharge process, remain unclear. The lithiation process of β-MnO2 has been systematically examined by first-principles calculations along with cluster expansion techniques. Five stable configurations during the lithium intercalation process are firstly determined, and the electrochemical voltages are from 3.47 to 2.77 eV, indicating the strongly correlated effects of the β-MnO2-LiMnO2 system. During the lithiation process, the changes in the lattice parameters are not symmetric. The analysis of electronic structures shows that Mn ions are in the mixed valence states of Mn(3+) and Mn(4+) during the lithiation process, which results in Jahn-Teller distortion in Mn(3+)O6 octahedra. Such results uncover the intrinsic origin of the asymmetric deformation during the charge-discharge process, resulting in the irreversible capacity fading during cycling. From the analysis of the thermal reduction of delithiated LixMnO2, the formation of oxygen is thermodynamically infeasible in the whole extraction process. Our results indicate that β-MnO2 has great potential as a cathode material for high capacity Li-ion batteries.

A novel surface-enhanced Raman scattering nanosensor for detecting multiple heavy metal ions based on 2-mercaptoisonicotinic acid functionalized gold nanoparticles

A novel, effective and simple surface-enhanced Raman scattering (SERS) nanosensor for selectively and sensitively detecting heavy metal ions in aqueous solution has been developed in the form of 2-mercaptoisonicotinic acid (2 MNA)-modified gold nanoparticles (AuNPs). Multiple heavy metal ions can be identified and quantified by using relative peak intensity ratios of selected vibrational bands in the SERS spectra of 2 MNA. Especially, concentration of Hg(2+) and Pb(2+) ions are determined by comparing the intensity ratios of the bands 1160/1230 cm(-1) for Hg(2+) and 861/815 cm(-1) (or 815/1392 cm(-1)) for Pb(2+), with detection limits of 3.4×10(-8) and 1.0×10(-7)M, respectively. 2 MNA-AuNPs sensors show a high selectivity for Hg(2+) without masking reagent, and they can also be highly selective for Pb(2+) when using sodium thiosulphate and l-cysteine as masking reagents. These results demonstrate that these 2 MNA-AuNPs nanosensors are promising candidates for in situ heavy metal ions detection and quantification, maybe even inside living cells.

Highly Reproducible Surface-Enhanced Raman Spectra on Semiconductor SnO2 Octahedral Nanoparticles

Highly reproducible surface-enhanced Raman scattering (SERS) spectra are obtained on the surface of SnO(2) octahedral nanoparticles. The spot-to-spot SERS signals show a relative standard deviation (RSD) consistently below 20 % in the intensity of the main Raman peaks of 4-mercaptobenzoic acid (4-MBA) and 4-nitrobenzenethiol (4-NBT), indicating good spatial uniformity and reproducibility. The SERS signals are believed to mainly originate from a charge-transfer (CT) mechanism. Time-dependent density functional theory (TD-DFT) is used to simulate the SERS spectrum and interpret the chemical enhancement mechanism in the experiment. The research extends the application of SERS and also establishes a new uniform SERS substrate.

Visible-Light Induced Photocatalytic Activity of Electrospun-TiO2 in Arsenic(III) Oxidation

In practical implementation of TiO2 semiconductors, utilization of their outstanding properties is mainly hindered by poor material quality and high operational costs. In this contribution, the electrospinning method was employed to fabricate N-doped mixed-crystalline TiO2 with exposed high-energy facets. The Ti oxide transformation process was thoroughly studied. During the mixed crystal structure formation process, the high-energy facets could be preserved due to the lower calcination temperature and the protective role of polyvinylpyrrolidone (PVP) in the electrospinning process. In addition, after calcination, the N doping, generated by the decomposition of PVP, extended the absorption spectrum of TiO2 to the visible region. These TiO2 fibers exhibited superior photooxidation of arsenite (III) to arsenate (V)in both the UV and visible light regions, mainly attributed to the exposure of high-energy facets, robust separation of photoexcited charge carriers between the anatase/rutile phases, and narrow band gap induced by the in situ N doping. Combining both robustness and scalability, the TiO2 fibers produced via this electrospinning process have the potential for a broad range of applications.

Quantitative analysis of mononucleotides by isotopic labeling surface-enhanced Raman scattering spectroscopy

A novel surface-enhanced Raman scattering (SERS) approach for accurate quantification of mononucleotides of deoxyribonucleic acid (DNA) is described. Reproducible SERS measurement was achieved by using isotopically labeled internal standard. By measuring the SERS spectra of mononucleotides and its isotope internal standard in combination with multivariate data analysis, the method was successfully applied to quantify mononucleotides. The independent validation of analyte concentrations gave a standard deviation of within 2%, which is comparable to HPLC result. Finally, a mixture of four mononucleotides of DNA was prepared to explore the possibility of quantifying the concentration of label-free, sequence-specific DNA strands by this approach. As compared to liquid chromatography/mass spectrometry (LC/MS), our method can be similarly precise but the SERS measurement is simple, rapid and potentially cheap.

Chemical Effects in SERS of Pyrazine Adsorbed on Au–Pd Bimetallic Nanoparticles: A Theoretical Investigation

Chemical enhancement in surface-enhanced Raman scattering (SERS) of pyrazine adsorbed on Au-Pd nanoclusters is investigated by using density functional theory. Changing Pd content in the bimetallic clusters enables modulation of the direct chemical interactions between the pyrazine and the clusters. The magnitude of chemical enhancement is correlated well with the induced polarizability for the complexes with low Pd content, which fails for the complexes with high Pd content. Furthermore, the dependence of chemical enhancement on cluster size and coupling is also described by the induced polarizability. Additionally, the chemical enhancement in the cluster-molecule-cluster junction is found to account for as much as 10(3), which suggests that a chemical mechanism might be more important than previously believed, in particular for Au-Pd bimetallic nanoparticle aggregates.